Here is what you can do:
1) Create a text box in the Document Header section. Ultimately, you'll set the Visible property to No. But you might want to leave it to Yes in the beginning so you can see what is going on.
2) Set the Name property of the text box to txtDocumentRunningTotal
3) Set the control source to: =1
4) Set the Running Sum property to Over Group
5) If you don't have a Division Footer, go to Sorting and Grouping and set the Footer to Yes
6) In the Division Footer Section, create another text box
7) Set the Name property of the text box to txtDocumentTotal
8) Set the control source to: txtDocumentRunningTotal
Leave the second text box visible and you have a count of the total unique Document names per division.
If all you want is the total count of unique documents across the whole report, just make a totals query with just the Document column. Group it and save the query. Then add a text field to your report and use the DCount Function ... set the control source to something like this: =DCount("Document","qryDocuments")
One of the two solutions should work for you.